CN114836798B - Preparation method of cobalt-molybdenum coating, electrode, water electrolysis device and household appliance applying preparation method - Google Patents
Preparation method of cobalt-molybdenum coating, electrode, water electrolysis device and household appliance applying preparation method Download PDFInfo
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- CN114836798B CN114836798B CN202110138591.9A CN202110138591A CN114836798B CN 114836798 B CN114836798 B CN 114836798B CN 202110138591 A CN202110138591 A CN 202110138591A CN 114836798 B CN114836798 B CN 114836798B
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- molybdenum
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- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 238000000576 coating method Methods 0.000 title claims abstract description 117
- 239000011248 coating agent Substances 0.000 title claims abstract description 115
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000005868 electrolysis reaction Methods 0.000 title claims description 18
- -1 electrode Substances 0.000 title description 5
- 238000004070 electrodeposition Methods 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000009713 electroplating Methods 0.000 claims abstract description 25
- 150000001868 cobalt Chemical class 0.000 claims abstract description 14
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims abstract description 11
- 239000011684 sodium molybdate Substances 0.000 claims description 29
- 235000015393 sodium molybdate Nutrition 0.000 claims description 29
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 29
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000001509 sodium citrate Substances 0.000 claims description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- ICYJJTNLBFMCOZ-UHFFFAOYSA-J molybdenum(4+);disulfate Chemical compound [Mo+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ICYJJTNLBFMCOZ-UHFFFAOYSA-J 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229960003975 potassium Drugs 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- SAXCKUIOAKKRAS-UHFFFAOYSA-N cobalt;hydrate Chemical compound O.[Co] SAXCKUIOAKKRAS-UHFFFAOYSA-N 0.000 claims 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 69
- 239000001257 hydrogen Substances 0.000 abstract description 68
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 68
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 98
- 229910052802 copper Inorganic materials 0.000 description 98
- 239000010949 copper Substances 0.000 description 98
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 48
- 238000000151 deposition Methods 0.000 description 43
- 230000008021 deposition Effects 0.000 description 43
- 238000007747 plating Methods 0.000 description 31
- DAYYOITXWWUZCV-UHFFFAOYSA-L cobalt(2+);sulfate;hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O DAYYOITXWWUZCV-UHFFFAOYSA-L 0.000 description 30
- 238000003756 stirring Methods 0.000 description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- 230000010287 polarization Effects 0.000 description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 14
- 238000005137 deposition process Methods 0.000 description 13
- 229910052697 platinum Inorganic materials 0.000 description 13
- 238000005238 degreasing Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000003822 epoxy resin Substances 0.000 description 12
- 229910002804 graphite Inorganic materials 0.000 description 12
- 239000010439 graphite Substances 0.000 description 12
- 238000000227 grinding Methods 0.000 description 12
- 238000005498 polishing Methods 0.000 description 12
- 229920000647 polyepoxide Polymers 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 150000001447 alkali salts Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- BYTCDABWEGFPLT-UHFFFAOYSA-L potassium;sodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[K+] BYTCDABWEGFPLT-UHFFFAOYSA-L 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a preparation method of a cobalt-molybdenum coating, an electrode, an electrolytic water device and household appliances applying the preparation method, wherein the preparation method of the cobalt-molybdenum coating comprises the following steps: and electrodepositing on the substrate by adopting an electrodeposition method to obtain a cobalt-molybdenum coating, wherein electroplating liquid adopted by the electrodeposition comprises cobalt salt, molybdenum salt and citrate. The cobalt-molybdenum coating can provide more active sites for electrocatalytic hydrogen evolution reaction, so that the cobalt-molybdenum coating has excellent catalytic hydrogen evolution activity, is favorable for reducing hydrogen evolution overpotential, can be applied to the field of electrolyzed water, and has the advantages of simple preparation method and low material cost.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to a preparation method of a cobalt-molybdenum coating, an electrode, a water electrolysis device and household appliances applying the preparation method.
Background
Hydrogen has the advantages of light weight, high heat value, clean combustion products and the like, and is considered as an ideal energy carrier. Hydrogen is becoming an important component of future energy sources, and can be used as fuel of fuel cells and as an energy storage medium for regulating wind energy and solar power generation systems. The method for industrially producing hydrogen mainly comprises the following steps: hydrogen production by synthesis gas or natural gas, hydrogen production by methanol pyrolysis, hydrogen production by coke oven gas, hydrogen production by water gas method, hydrogen production by electrolysis of water, etc. Compared with other hydrogen production methods, the water electrolysis hydrogen production method can produce hydrogen with higher purity, and is widely adopted in a plurality of industries.
The electrolyzed water mainly releases oxygen on the anode and hydrogen on the cathode when the sodium (potassium) hydroxide solution is electrolyzed. Hydrogen gas is also available when sodium hydroxide is produced by electrolysis of aqueous sodium chloride solutions. The field of hydrogen production by water electrolysis generally adopts a method of loading a catalyst on a cathode to improve the electrolysis efficiency. The existing catalysts used for the water electrolysis cathode are mostly noble metals such as platinum base and ruthenium base or composite materials thereof, and although the noble metal composite materials have better electrocatalytic hydrogen evolution capability, the noble metal composite materials are influenced by reserve content and are relatively expensive, so that the development and the application of the noble metal composite materials are limited. In order to reduce the cost on the catalyst in the electrolysis process, many researches are attempted to use non-noble metals and composite materials thereof to replace noble metals as cathode catalysts, but the hydrogen evolution overpotential of the materials has higher problem, and the hydrogen evolution catalytic activity needs to be improved.
Disclosure of Invention
The present invention aims to solve at least one of the above technical problems in the prior art. Therefore, the invention provides a preparation method of the cobalt-molybdenum coating, and the prepared cobalt-molybdenum coating has better catalytic activity on electrolytic hydrogen evolution and low hydrogen evolution overpotential.
The invention also provides an application of the cobalt-molybdenum coating in hydrogen production by water electrolysis, an electrode, an electrolytic water device and household appliances applying the cobalt-molybdenum coating preparation method.
Specifically, the first aspect of the invention provides a preparation method of a cobalt-molybdenum coating, which comprises the following steps: and electrodepositing on a substrate by adopting an electrodeposition method to obtain a cobalt-molybdenum coating, wherein the electroplating solution adopted by the electrodeposition contains cobalt salt, molybdenum salt and citrate, the mass ratio of the molybdenum salt to the cobalt salt is 1:3-6.5, and the pH value of the electroplating solution is 8-9.
The preparation method of the cobalt-molybdenum coating according to the first aspect of the invention has at least the following beneficial effects:
The plating solution adopted by the invention contains two transition metal elements of Co and Mo, and Co and Mo can form a cobalt-molybdenum plating layer by means of induction coprecipitation (Mo is deposited from the plating solution under the induction of Co). The cobalt-molybdenum coating can provide more active sites for electrocatalytic hydrogen evolution reaction, effectively adsorb hydrogen atoms, has good catalytic hydrogen evolution activity, and is beneficial to reducing hydrogen evolution overpotential.
According to one embodiment of the invention, the ratio of the amounts of the substances of the molybdenum salt and the cobalt salt is 1:4 to 6.
According to one embodiment of the invention, the ratio of the amounts of the substances of the molybdenum salt and the cobalt salt is 1:4.5 to 5.
According to one embodiment of the present invention, the concentration of the cobalt salt in the plating solution is 0.1mol/L to 0.2mol/L, and the concentration of the molybdenum salt is 0.03mol/L to 0.05mol/L.
According to one embodiment of the present invention, the concentration of the cobalt salt in the plating solution is 0.15mol/L to 0.19mol/L, and the concentration of the molybdenum salt is 0.033mol/L to 0.043mol/L.
According to one embodiment of the present invention, the concentration of the citrate in the plating solution is 0.07mol/L to 0.15mol/L.
The citrate can produce excitation effect on Co and Mo induced coprecipitation, and is beneficial to Mo deposition.
According to one embodiment of the present invention, the concentration of the citrate in the plating solution is 0.077mol/L to 0.12mol/L.
According to one embodiment of the invention, the pH value of the electroplating solution is regulated and controlled by adding a pH regulator, wherein the pH regulator can adopt general acid, acid salt, alkali or basic salt, so long as the deposition of Co and Mo and the structure and performance of a cobalt-molybdenum coating are not damaged. As an example, the pH adjustor may employ sulfuric acid, sulfuric acid salt, hydrochloric acid, sodium hydroxide, potassium hydroxide, or the like.
According to one embodiment of the present invention, the cobalt salt comprises at least one of cobalt sulfate and its hydrates, cobalt chloride and its hydrates, cobalt acetate and its hydrates, cobalt nitrate and its hydrates.
According to one embodiment of the present invention, the molybdenum salt includes at least one of molybdenum sulfate and its hydrate, sodium molybdate and its hydrate, potassium molybdate and its hydrate, ammonium molybdate and its hydrate.
According to one embodiment of the present invention, the cobalt salt is cobalt sulfate hexahydrate; the molybdenum salt is sodium molybdate.
According to one embodiment of the invention, the citrate is a general purpose water-soluble citrate, such as an alkali metal citrate, provided that it does not affect the deposition of Co, mo and the formation of the cobalt-molybdenum coating. Since metal ions in the transition metal citrate may also participate in the deposition, a transition metal citrate should not be used.
According to one embodiment of the invention, the citrate comprises at least one of sodium citrate and its hydrate, potassium citrate and its hydrate.
According to one embodiment of the invention, the electrodeposition employs a current density of 100mA/cm 2 or more.
The cobalt-molybdenum coating deposited and formed under the current density of more than or equal to 100mA/cm 2 has good hydrogen evolution catalytic activity, and the hydrogen evolution overpotential can be reduced to below 105 mV.
According to one embodiment of the invention, the current density is 100mA/cm 2～130mA/cm2.
In the current density range of 100-130 mA/cm 2, the formed cobalt-molybdenum coating has good hydrogen evolution catalytic activity, and meanwhile, the influence of hydrogen evolution overpotential of the cobalt-molybdenum coating along with the current density is small; and when the current density is too high, blackening and overburning occur, and the energy consumption is higher. Therefore, the current density is 100mA/cm 2～130mA/cm2 for comprehensive consideration of coating quality, catalytic performance, energy conservation and cost reduction.
According to one embodiment of the invention, the current density is 110mA/cm 2～130mA/cm2.
According to one embodiment of the invention, the electrodeposition time is 10min to 40min.
According to one embodiment of the invention, the electrodeposition time is 20min to 30min.
According to one embodiment of the present invention, the substrate may be an electrode substrate commonly used in the art, so long as the substrate does not react with the components of the plating solution, and does not affect the deposition of Co and Mo and the structure and performance of the cobalt-molybdenum plating. By way of example, the substrate may be copper, carbon steel, titanium, cobalt, nickel, stainless steel, or carbon.
According to one embodiment of the invention, the temperature is normal temperature during the electrodeposition process.
According to one embodiment of the invention, the temperature during the electrodeposition is 15-35 ℃.
According to one embodiment of the invention, the temperature during the electrodeposition is 25 ℃ to 30 ℃.
According to one embodiment of the invention, the temperature during the electrodeposition is 26-27 ℃.
According to one embodiment of the invention, the electrodeposition is carried out in stirring at a speed of 350rpm to 450rpm.
According to the invention, the thermal motion state of ions in the electroplating liquid in the deposition process is kept consistent by stirring, the deposition effect is improved, and the uniformity of materials is enhanced.
According to one embodiment of the invention, the electrodeposition is carried out in stirring at a speed of 380rpm to 420rpm.
According to one embodiment of the invention, the stirring speed is 400rpm.
According to one embodiment of the invention, the cobalt-molybdenum coating has a thickness of 15 μm to 30 μm.
According to one embodiment of the present invention, the cobalt-molybdenum plating layer contains Mo and Co in a mass ratio of 1:2 to 5.
According to one embodiment of the invention, the mass ratio of Mo to Co is 1:3 to 4.
According to one embodiment of the invention, the ratio of the amounts of the substances Mo and Co is 1:3.3.
According to one embodiment of the invention, the cobalt-molybdenum coating contains Mo, co, C and O.
According to one embodiment of the invention, the mass percentage of Mo and Co in the cobalt-molybdenum coating is 20-30%, 40-50%, and the balance is C and O.
According to one embodiment of the invention, the mass percentages of C and O are respectively 10% -15% and 5% -10%.
In a second aspect the invention provides the use of a cobalt-molybdenum coating produced according to the above-described production method in the electrolysis of water.
In a third aspect the invention provides an electrode comprising a substrate and a cobalt-molybdenum coating deposited on the substrate, the cobalt-molybdenum coating being produced by the above-described production method.
According to one embodiment of the invention, the substrate may be a conductive electrode substrate commonly used in the art, such as copper, carbon steel, titanium, cobalt, nickel, stainless steel or carbon.
A fourth aspect of the present invention provides an electrolytic water device comprising an electrode as described above.
A fifth aspect of the present invention provides an electric home appliance having the water electrolysis apparatus as described above.
The invention has at least the following beneficial effects:
According to the invention, the formula components of the electroplating solution are optimized, and Co and Mo in the electroplating solution form a cobalt-molybdenum coating by inducing coprecipitation in the electrodeposition process. The cobalt-molybdenum coating can provide more active sites for electrocatalytic hydrogen evolution reaction, has good catalytic hydrogen evolution activity, and is beneficial to reducing hydrogen evolution overpotential.
Experiments prove that the cobalt-molybdenum coating provided by the invention has good catalytic activity in electrolytic water hydrogen evolution reaction, and hydrogen evolution overpotential in a KOH solution of 1mol/L can be reduced to 105mV or below, and has lower hydrogen evolution overpotential.
In addition, the preparation method is simple, and the electrocatalytic hydrogen evolution catalytic material is prepared from low-cost Co and Mo transition metals, so that the cost is reduced compared with the noble metal catalytic material.
Drawings
FIG. 1 is a scanning electron microscope image of the cobalt-molybdenum coating of example 1 at different magnifications, wherein (a) is 1000 times and (b) is 3000 times;
FIG. 2 is an X-ray energy spectrum of the cobalt-molybdenum coating of example 1;
FIG. 3 is a graph of voltage versus current density for the cobalt-molybdenum coatings of examples 1 and 2;
FIG. 4 is a Tafil plot of the cobalt-molybdenum coatings of example 1 and example 2;
FIG. 5 is a graph of overpotential of a cobalt-molybdenum coating versus concentration of cobalt sulfate hexahydrate in a plating solution;
FIG. 6 is a graph of overpotential of a cobalt-molybdenum coating versus mass ratio of cobalt sulfate hexahydrate to sodium molybdate in a plating solution;
FIG. 7 is a graph of overpotential versus current density for a cobalt-molybdenum coating.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative only and are not to be construed as limiting the invention.
The test methods used in the examples are conventional methods unless otherwise specified; materials, reagents, and the like used, unless otherwise specified, are commercially available; the operations in the examples were all performed at normal temperature.
Example 1
And (3) taking red copper as a cathode and graphite as an anode, and preparing a cobalt-molybdenum coating on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate 40g/L, sodium molybdate 7g/L, sodium citrate 20g/L, and pH approximately 8. The deposition time was 20min, and the deposition current density was 110mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The cobalt-molybdenum coating of the embodiment is silvery white, has obvious metallic luster and has a thickness of 15-30 mu m. The microscopic morphology of the cobalt-molybdenum coating of this example was observed using a scanning electron microscope, and the results are shown in fig. 1. The result shows that the surface of the cobalt-molybdenum coating is dispersed with a cluster of spherical small particles with the cluster size of 0.5-1 mu m, has larger specific surface area, can provide more active sites for the hydrogen evolution process, and is favorable for the hydrogen evolution reaction. The elements of the cobalt-molybdenum coating are analyzed, and the X-ray energy spectrum is shown in figure 2. Fig. 2 shows that the cobalt-molybdenum coating mainly contains Co, mo, C, O elements, wherein the mass percentages of Co element, mo element and O element are respectively as follows: 50%, 25% and 10%, the balance being C.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures a polarization curve, the potential interval is from plating open circuit potential (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the Tafil curve is obtained through calculation and transformation according to the LSV test result.
The voltage versus current density plot and tafel plot of the cobalt-molybdenum coating of this example in 1mol/L KOH solution are shown in fig. 3 and 4, respectively.
The test results show that the hydrogen evolution overpotential eta 10 (namely the corresponding voltage value in the state of 10mA/cm 2 of current density) of the cobalt-molybdenum coating of the embodiment is 0.090V relative to a standard hydrogen electrode, and the Tafil slope is 77.17mV/dec, and the cobalt-molybdenum coating has lower hydrogen evolution overpotential and smaller Tafil slope.
Example 2
And (3) taking red copper as a cathode and graphite as an anode, and preparing a cobalt-molybdenum coating on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate 50g/L, sodium molybdate 9g/L, sodium citrate 30g/L, and pH approximately 9. The deposition time was 30min, and the deposition current density was 130mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures a polarization curve, the potential interval is from plating open circuit potential (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the Tafil curve is obtained through calculation and transformation according to the LSV test result.
The voltage versus current density plot and tafel plot of the cobalt-molybdenum coating of this example in 1mol/L KOH solution are shown in fig. 3 and 4, respectively.
The test result shows that the hydrogen evolution overpotential eta 10 of the cobalt-molybdenum coating of the embodiment is 0.088V relative to a standard hydrogen electrode, the Tafil slope is 82.01mV/dec, and the cobalt-molybdenum coating has lower hydrogen evolution overpotential and smaller Tafil slope and has good hydrogen evolution catalytic performance.
Example 3
And (3) taking red copper as a cathode and graphite as an anode, and preparing a cobalt-molybdenum coating on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: 10g/L (or 20g/L, 30g/L, 40g/L, 50 g/L) of cobalt sulfate hexahydrate, 6.5g/L of sodium molybdate, 25g/L of sodium citrate and pH of about 8; the deposition time was 25min, and the deposition current density was 125mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures a polarization curve, the potential interval is from the open circuit potential (VS HgO) of the plating layer to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, so that the relationship between the hydrogen evolution overpotential and the concentration of cobalt sulfate hexahydrate in the electroplating solution is shown in figure 5. FIG. 5 shows that the hydrogen evolution overpotential of the cobalt-molybdenum coating gradually decreases with increasing concentration of cobalt sulfate hexahydrate, reflecting that the catalytic hydrogen evolution performance of the cobalt-molybdenum coating increases with increasing concentration of Co in the plating solution over a range.
Example 4
And (3) taking red copper as a cathode and graphite as an anode, and preparing a cobalt-molybdenum coating on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate concentration was 40g/L, sodium molybdate 10g/L, cobalt sulfate hexahydrate to sodium molybdate mass ratio (cobalt sulfate hexahydrate/sodium molybdate) was 4, the corresponding cobalt sulfate hexahydrate to sodium molybdate mass ratio was 3.1, sodium citrate concentration was 25g/L, and pH was about 8.5. The deposition time was 25min, and the deposition current density was 125mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures the polarization curve, the potential interval is from the open circuit potential (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, and the result is shown in figure 6.
Example 5
This embodiment is similar to embodiment 4, except that: the mass ratio of cobalt sulfate hexahydrate to sodium molybdate in the plating solution of this example was 6, and the corresponding mass ratio of cobalt sulfate hexahydrate to sodium molybdate was 4.7.
Specifically, red copper is used as a cathode, graphite is used as an anode, and a cobalt-molybdenum coating is prepared on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate at a concentration of 40g/L, sodium molybdate at a concentration of 6.67g/L, sodium citrate at a concentration of 25g/L, and a pH of about 8.5. The deposition time was 25min, and the deposition current density was 125mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures the polarization curve, the potential interval is from the open circuit potential (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, and the result is shown in figure 6.
Example 6
This embodiment is similar to embodiment 4, except that: the mass ratio of cobalt sulfate hexahydrate to sodium molybdate in the plating solution of this example was 8, and the corresponding mass ratio of cobalt sulfate hexahydrate to sodium molybdate was 6.3.
Specifically, red copper is used as a cathode, graphite is used as an anode, and a cobalt-molybdenum coating is prepared on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate at a concentration of 40g/L, sodium molybdate at a concentration of 5g/L, sodium citrate at a concentration of 25g/L, and a pH of about 8.5. The deposition time was 25min, and the deposition current density was 125mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures the polarization curve, the potential interval is from the open circuit potential (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, and the result is shown in figure 6.
Example 7
This embodiment is similar to embodiment 4, except that: the mass ratio of cobalt sulfate hexahydrate to sodium molybdate in the plating solution of this example was 10, and the corresponding mass ratio of cobalt sulfate hexahydrate to sodium molybdate was 7.8.
Specifically, red copper is used as a cathode, graphite is used as an anode, and a cobalt-molybdenum coating is prepared on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate at a concentration of 40g/L, sodium molybdate at a concentration of 4g/L, sodium citrate at a concentration of 25g/L and at a pH of about 8.5. The deposition time was 25min, and the deposition current density was 125mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures the polarization curve, the potential interval is from the open circuit potential (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, and the result is shown in figure 6.
The graphs of the relationship between the hydrogen evolution overpotential obtained in examples 4 to 7 and the mass ratio of cobalt sulfate hexahydrate to sodium molybdate in the plating solution, that is, the graph of fig. 6 shows that the hydrogen evolution overpotential of the cobalt-molybdenum plating layer increases after decreasing with increasing Co/Mo in the range of the mass ratio of cobalt sulfate hexahydrate to sodium molybdate=4 to 10, the hydrogen evolution overpotential of the cobalt-molybdenum plating layer is 100mV or less when the mass ratio of cobalt sulfate hexahydrate to sodium molybdate=4 to 8, and the minimum hydrogen evolution overpotential is obtained when the mass ratio of cobalt sulfate hexahydrate to sodium molybdate=about 6. The phenomenon may be that when more Mo element exists in the electroplating solution, the large-volume Mo atoms occupy a large amount of space in the plating layer due to different sizes of Co and Mo, and deposition of Co atoms with relatively smaller volume is affected, so that the performance of the plating layer is reduced; and when the Mo element in the electroplating solution is less, the plating performance cannot be greatly improved.
Example 8
And (3) taking red copper as a cathode and graphite as an anode, and preparing a cobalt-molybdenum coating on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate 40g/L, sodium molybdate 6.5g/L, sodium citrate 25g/L, and pH approximately 8. The deposition time was 25min, and the deposition current density was 50mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures the polarization curve, the potential interval is from the open circuit potential of the plating (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, and the result is shown in figure 7.
Example 9
This embodiment is similar to embodiment 8, except that: the current density used for electrodeposition in this example was 75mA/cm 2.
Specifically, red copper is used as a cathode, graphite is used as an anode, and a cobalt-molybdenum coating is prepared on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate 40g/L, sodium molybdate 6.5g/L, sodium citrate 25g/L, and pH approximately 8. The deposition time was 25min, and the deposition current density was 75mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures the polarization curve, the potential interval is from the open circuit potential of the plating (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, and the result is shown in figure 7.
Example 10
This embodiment is similar to embodiment 8, except that: the current density used for electrodeposition in this example was 100mA/cm 2.
Specifically, red copper is used as a cathode, graphite is used as an anode, and a cobalt-molybdenum coating is prepared on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate 40g/L, sodium molybdate 6.5g/L, sodium citrate 25g/L, and pH approximately 8. The deposition time was 25min, and the deposition current density was 100mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures the polarization curve, the potential interval is from the open circuit potential of the plating (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, and the result is shown in figure 7.
Example 11
This embodiment is similar to embodiment 8, except that: the current density used for electrodeposition in this example was 125mA/cm 2.
Specifically, red copper is used as a cathode, graphite is used as an anode, and a cobalt-molybdenum coating is prepared on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate 40g/L, sodium molybdate 6.5g/L, sodium citrate 25g/L, and pH approximately 8. The deposition time was 25min, and the deposition current density was 125mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures the polarization curve, the potential interval is from the open circuit potential of the plating (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, and the result is shown in figure 7.
Example 12
This embodiment is similar to embodiment 8, except that: the current density used for electrodeposition in this example was 150mA/cm 2.
Specifically, red copper is used as a cathode, graphite is used as an anode, and a cobalt-molybdenum coating is prepared on the red copper by deposition through an electrodeposition method. The electroplating solution used for electrodeposition comprises the following components: cobalt sulfate hexahydrate 40g/L, sodium molybdate 6.5g/L, sodium citrate 25g/L, and pH approximately 8. The deposition time was 25min, and the deposition current density was 150mA/cm 2.
The deposition process was assisted by stirring with a magnetic stirrer at a stirring speed of 400rpm. The red copper has the size of 10 multiplied by 3mm, the red copper is subjected to sample sealing by epoxy resin after being welded with a lead, the exposed effective area is ensured to be 1cm 2, and the red copper is subjected to grinding, polishing, acid washing, degreasing and drying treatment before electrodeposition.
And after the electrodeposition is finished, a cobalt-molybdenum coating is obtained on the surface of the red copper, and the red copper is cleaned by pure water and dried for standby.
The Cinhua 660e electrochemical workstation is adopted to detect the cobalt-molybdenum coating in a KOH solution of 1mol/L, a three-electrode mode is adopted, the working electrode is a red copper electrode deposited with the cobalt-molybdenum coating in the embodiment, the counter electrode is a platinum electrode, and the reference electrode is an HgO electrode. The LSV measures the polarization curve, the potential interval is from the open circuit potential of the plating (VS HgO) to-0.3V (VS HgO), the scanning speed is 0.001V/s, and the hydrogen evolution overpotential is calculated according to the polarization curve, and the result is shown in figure 7.
The relationship between hydrogen evolution overpotential and current density obtained in examples 8 to 12 is shown in FIG. 7. The test result shows that the hydrogen evolution overpotential of the cobalt-molybdenum coating is increased when the current density is too small, the smaller hydrogen evolution overpotential can be obtained after the current density is more than or equal to 100mA/cm 2, and the hydrogen evolution overpotential is slowly reduced along with the increase of the current density between 100mA/cm 2～150mA/cm2. In practical experiments, blackening over-burning occurs when the current density is more than 130mA/cm 2, and the structure and stability of the plating layer are affected. Considering the hydrogen evolution overpotential and the overburning phenomenon comprehensively, the current density can be selected to be 100mA/cm 2～130mA/cm2, and further can be selected to be 110mA/cm 2～130mA/cm2.
The present invention has been described in detail with reference to the embodiments, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention.
Claims (13)
1. The preparation method of the cobalt-molybdenum coating is characterized in that: the method comprises the following steps:
Electrodepositing on a substrate by adopting an electrodeposition method to obtain a cobalt-molybdenum coating, wherein a solute of an electroplating solution adopted by the electrodeposition consists of cobalt salt, molybdenum salt, citrate and a pH regulator, the mass ratio of the molybdenum salt to the cobalt salt is 1:3-6.5, and the pH of the electroplating solution is 8-9;
In the electroplating solution, the concentration of the cobalt salt is 0.1 mol/L-0.2 mol/L, and the concentration of the molybdenum salt is 0.03 mol/L-0.05 mol/L; the concentration of the citrate is 0.07 mol/L-0.15 mol/L;
the current density adopted by the electrodeposition is more than or equal to 100 mA/cm 2;
the electrodeposition time is 10-40 min;
the thickness of the cobalt-molybdenum coating is 15-30 mu m;
The cobalt-molybdenum coating contains Mo and Co, and the mass ratio of the Mo to the Co is 1:2-5.
2. The method for preparing a cobalt-molybdenum coating according to claim 1, wherein: the mass ratio of the molybdenum salt to the cobalt salt is 1:4-6.
3. The method for preparing a cobalt-molybdenum coating according to claim 1, wherein: the cobalt salt comprises at least one of cobalt sulfate and hydrate thereof, cobalt chloride and hydrate thereof, cobalt acetate and hydrate thereof, and cobalt nitrate and hydrate thereof.
4. The method for preparing a cobalt-molybdenum coating according to claim 1, wherein: the molybdenum salt comprises at least one of molybdenum sulfate and its hydrate, sodium molybdate and its hydrate, potassium molybdate and its hydrate, ammonium molybdate and its hydrate.
5. The method for preparing a cobalt-molybdenum coating according to claim 1, wherein: the citrate includes at least one of sodium citrate and its hydrate, potassium citrate and its hydrate.
6. The method for preparing a cobalt-molybdenum coating according to claim 1, wherein: the current density was 100 mA/cm 2~130 mA/cm2.
7. The method for preparing a cobalt-molybdenum coating according to claim 1, wherein: the mass ratio of the Mo to the Co is 1:3-4.
8. The method for preparing a cobalt-molybdenum coating according to claim 1, wherein: the cobalt-molybdenum coating contains Mo, co, C and O.
9. The method for producing a cobalt-molybdenum coating according to claim 8, characterized in that: the mass percentages of Mo and Co in the cobalt-molybdenum coating are 20% -30%, 40% -50% and the balance is C and O.
10. Use of the cobalt-molybdenum coating prepared by the preparation method of any one of claims 1-9 in electrolysis of water.
11. An electrode, characterized in that: comprising a substrate and a cobalt-molybdenum coating deposited on the substrate, the cobalt-molybdenum coating being produced by the production method according to any one of claims 1 to 9.
12. The water electrolysis device is characterized in that: the electrode according to claim 11 is contained in the water electrolysis device.
13. Household electrical appliances, its characterized in that: the household electrical appliance comprises the water electrolysis device according to claim 12.
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| CN114921823A (en) * | 2021-02-01 | 2022-08-19 | 芜湖美的厨卫电器制造有限公司 | Preparation method of coating, electrode and household appliance applying preparation method |
| CN114921689A (en) * | 2021-02-01 | 2022-08-19 | 芜湖美的厨卫电器制造有限公司 | Cobalt-molybdenum-based composite material, hydrogen evolution electrode, preparation method of cobalt-molybdenum-based composite material and application of cobalt-molybdenum-based composite material in hydrogen production by water electrolysis and household appliances |
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| US2653127A (en) * | 1946-11-08 | 1953-09-22 | Brenner Abner | Methods of and baths for electrodepositing cobalt or cobalt-molybdenum alloys |
| JP4085772B2 (en) * | 2002-10-21 | 2008-05-14 | アタカ大機株式会社 | Alloy electrode for hydrogen generation and method for producing the same |
| KR100635300B1 (en) * | 2005-05-03 | 2006-10-19 | 한국과학기술연구원 | Method of preparing crystalline molybdenium-cobalt alloy thin film using electrodeposition |
| TWI593548B (en) * | 2015-01-09 | 2017-08-01 | Jx Nippon Mining & Metals Corp | Attached to the metal substrate |
| JP6072962B2 (en) * | 2015-01-09 | 2017-02-01 | Ｊｘ金属株式会社 | Metal substrate with plating |
| US11459664B2 (en) * | 2017-07-21 | 2022-10-04 | Temple University—Of the Commonwealth System of Higher Education | Multi-metal catalysts and devices and methods of use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114921823A (en) * | 2021-02-01 | 2022-08-19 | 芜湖美的厨卫电器制造有限公司 | Preparation method of coating, electrode and household appliance applying preparation method |
| CN114921689A (en) * | 2021-02-01 | 2022-08-19 | 芜湖美的厨卫电器制造有限公司 | Cobalt-molybdenum-based composite material, hydrogen evolution electrode, preparation method of cobalt-molybdenum-based composite material and application of cobalt-molybdenum-based composite material in hydrogen production by water electrolysis and household appliances |
Non-Patent Citations (1)
| Title |
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| Electrocatalytic Properties of Co-Mo Alloys Electrodeposited from a Citrate-Pyrophosphate Electrolyte;V. S. Kublanovsky等;《 Electrocatalysis》;第5卷;372-378 * |
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